O-lower alkyl-o-(2 - carbisopropoxyphenyl) phosphoric acid diester amides

ABSTRACT

O-LOWER ALKYL-O-(2-CARBISOPROPOXYPHENYL) PHOSPHORIC ACID DIESTER AMIDES WHEREIN THE AMIDE GROUP MAY BE MONO-SUBSTITUTED WITH A LOWER ALKYL RADICAL, WHICH POSSES ARTHROPODIIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, PROPERTIES AND NEW METHOS FOR THEIR PREPARTION.

United States Patent 01 h-ce 3,660,540 Patented May 2, 1972 9 Claims ABSTRACT OF THE DISCLOSURE O-lower alkyl-O-(Z-carbiSopropoxyphenyl) phosphoric acid diester amides wherein the amide'group may. be mono-substituted with a lower alkyl radical, which possess arthropodicidal, especially acaricidal and insecticidal, properties and new methods for their preparation. v .7

The present invention relates to and has for, its 'objects the provision of particularnewvO-loweralkyl-Q42- carbisopropoxyphenyl) phosphoric acid diester,,amides wherein the amide group may be mono-substituted with a lower alkyl radical, which possess arthropodicidaLgespecially insecticidal and acaricidal, properties, active compositions in the form of mixturesof such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using suchcom pounds in a new Way especially for cornbatin'gpests, e.g. arthropods, with other and further objects vbecoming apparent from a study of the within specification and accompanying examples.

his knownthat N,N-dimethylamido-o ethyl and bis- (N,N-dimethylamido )-phosphorylsalicylic acid ethylesters as well as 0,0-dialkylthionophosphorylsalicylic' acid esters exhibit insecticidal properties (see German Patent Specifications 814,152 and 811,514, as well as R.L.'-Metcalf Organic Insecticides Interscience Publishers, New York, 1955).

The present invention provides new O-lower alkyl-O- (Z-carbisopropoxyphenyl) phosphoric acid diester amides which may also be identified as amidophosphorylsalicylic acid esters of the formula 'OOR in which:

R is a straight or branched chain lower alkylira dicaland R is hydrogen or straight or branched chain lower alkyl radical,

(a "an amidothionophosphorylsalicylic acid ester of the formula J CO-O-GH OH is oxidized with selenium dioxide, or in another of which (b) an O-alkyl-O-(Z-carbalkoxyphenyl)-phosphoric acid diester monohalide of the formula Hal . I COO-CH(CHa)2 (III) is reacted-with ammonia or a primary amine of the formula it v I NHR' in the presence of an acid-binding agent, or in a third of which (c) an -al'kylphosphoric acid ester amide chloride of v ,the general formula ll Hal-P NHR is; reacted :with salicylic acid iso-propyl ester,:or an alkali metalror ammonium'salt thereof, optionally in the'presence of an acid-binding agent. 7

lnathe-Formulae II to V, R and R have the meanings statedabove the Formula I and Hal stands fora halogen atom., Surprisingly, the amidophosphorylsalicylic acid esters according to theinvention show considerably higher insecticidal and acaricidal activity, especially, excellent activity against biting and sucking 'insectsthan the =N,N-dimethylamid'o-O-ethyl or bis-(N,N-dimethylamido)-phosphorylsalicylic acid ethyl esters or 0,0-dialky1thionophosphorylsalicylic acid ethyl esters known in the-prior art 'which are the chemically closest compounds of the same type of activity. The invention therefore represents a'valuable contribution to the. art.

If 0 methyl-O'-(Z-oarbisopropoxyphenyl)-thionophosphoric acid diester amide and selenium dioxide are used as starting materials for the process according to process variant (a), the reaction course can be represented by the following equation:

The starting materials to be used for the process are clearly defined by the Formulae II to V. Preferably, R, in the foregoing formulae stands for branched or un- 3 branched alkyl with 1 to 4 and especially 1 to 3 carbon atoms, i.e. methyl, ethyl, nor iso-propyl; R preferably stands for alkyl of 1 to 4 carbon atoms, and especially 1 to 3, but most preferably stands for hydrogen. Hal preferably denotes chlorine.

As examples of the amidothionophosphorylsalicylic acid esters of the Formula II which can be used, there are mentioned in particular:

O-methyl-, O-ethy1-, N-methyl-O-methyl-, N-methyl-O- ethyl-, N-ethyl-O-methyl-, N-ethyl-O-ethyl-, N-propyl- O-methyl-, N-iso-propyl-O-methyl-, N-propyl-O-ethyland N-iso-propyl-O-ethyl-O-(Z-carbisopropoxyphenyD- thionophosphoric acid diester amides.

As examples of phosphoric acid ester halides or amide halides of Formula III or V, there are mentioned in particular:

O-methyland O-ethyl-O-(2-carbisopropoxyphenyl)-phosphoric acid diester chloride, and N-rnethyl-O-methyl-, N-ethy1-O-ethy1-, N-propyl O methyl-, N-propyl-O- ethyl-, N-iso-propyl- O methyland N-iso-propyl-O- ethylphosphon'c acid ester amide chloride.

Some of the phosphoric acid derivatives of Formulae I and V required as starting materials for the process according to the invention are known in the literature and all can be prepared according to known processes. The amidothionophosphorylsalicylic acid esters of Formula II can be obtained from O-alkyl-O(2-carbisopropoxyphenyl)-thionophosphoric acid diester monohalides of the formula with ammonia or primary amines of the Formula IV in organic solvents or in water (as described in Germant patent application P 16 68 047.0).

\In Formula VI, R and Hal have the meanings stated above.

As solvents or diluents which may be used in the processes according to the invention, all inert organic solvents or diluents are suitable. These include all aliphatic and aromatic hydrocarbons (which may be chlorinated), such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, ethers, such as diethyl ether, dibutyl ether and dioxane, ketones, such as acetone, methylethyl-, methylisopropyland methylisobutyl ketone, and also, nitriles, such as acetonitrile. The reaction solutions are in most cases stirred for some hours, and are then worked up according to customary methods. As acid-binding agents all customary acid acceptors are suitable. Particularly suitable are alkali metal carbonates such as sodium and potasium carbonate, alkali metal alcoholates such as sodium or potassium methylate or ethylate, and aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperatures can be carried within a fairly wide range. In general, the work is carried out at from to 100 C., preferably at from 30 to 60 C.

The reactions are, in general, carried out at normal pressure.

When carrying out process variant (a) according to the invention, namely the selenium dioxide oxidation, the selenium dioxide is desirably used in excess of the stoichiometrically equimolar requirements, e.g. a 50 to 150% excess has proved advantageous. In process variants (b) and (c), the starting materials are preferably used in approximately equimolar proportions.

As mentioned briefly above, the new products are dis- 4 tinguished by outstanding effectiveness against plant pests, household pests and pests of stored products, particularly against biting. and sucking insects and mites. The pesticidal efiect sets in rapidly and is long-lasting.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae) the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosz'phum padi), the pea aphid (Macrosiphum pz'si) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid( Cryptomyzus korschelti), the mealy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the cotton bug (Dysdercus intermedius), the bed bug (Simex lectularius) the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus, and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the browntail moth (Euproctis chrysorrhaea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra bralrsicae) and the cutworm (Agrotis segetum), the large white butterfly (Pieris bmrsicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Laphyg'ma frugiperda) and cotton worm (Pradenia litura), the ermine moth (Hyponomeuta paa'ellw), the Mediter ranean flour moth (Ephestia kt'lhniella) and greater wax moth (Galleria mellonella), and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius=Calandra granaria), the Colordo beetle (Leptinotarsw decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochlearz'ae) the blossom beetle (M eligethes aeneus), the raspberry beetle (Byturus tomenlosus), the bean weevil (Bruchidius=Acanthoscelides obtectus), the leather beetle (Trogoderma granarium), the flour beetle (T ribolium casraneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworm (Agriotes spec.) and larvae of the cockchafer (Melolontha m-elolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach Periplaneza amerz'cana), Madeira cockroach (Leucophaea or Rhyparobia madez'rae), Oriental cockroach (Blatza orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasz'us niger), and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosaphz'la melanogaster), the Mediterranean fruit fly (Ceralz'tis capitata), the house fly (Musca domestica), the little house fly (Fannz'a canicularis), the black blow fly (Phormia aegina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans) further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles srephensi); and the like.

With the mites (Acari) contemplated hereinthereare classed, 'in particular, the spider mites Tetranychidae) such as the two-spottedspider mite (T etranychus 'telarius=.Tet ranychus altha eaeor T etranychus urticae') and the European red mite (Pardtetranychus pil sus=Pan0 r ych'uls t'tlm'i), blister mines, for example the current blister mite (Eriophyes. ribis); and tarsonemids, for example the board mite (Hemita'rsonemus latizs) and the cyclam'en mite Tarsonemus pallidus); finaly, ticks, such'as the relapsing fever tick (Ofm'thddorus mbubatafland; the like. f .T 'j 1 When applied against household pestsand pests of stored products, particularly flies and mosquitoes, the products are distinguished by an outstanding residual effect onwood and clay as well as by a good stability to alkali or limed substrates.

The active compounds according to the instant invention can be utilized, if desired,'-in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticidal diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticidal formulations or compositions, e.g. conventional pesticidal dispersible carrier vehicles such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agentsygranules, etc. These are prepared in known manner,.for instance by extending the active compounds with conventional"pesticidal dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use'of-carrieryehicle assistants, e.g. conventional pesticidal surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where wateris used as diluent; organic solvents may be added as auxiliary solvents. The following may bechieflyconside'red for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluentcar'rier's,ineluding inert organic solvents, such as aromatic 'hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e,g. chlorobenzenes, etc.), 'parafiins (e.g. petroleum fractions), chlorinated aliphatichydrocarbons (e.g. methylene chloride, etc.),,alcohols (e.g. methanol,,ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.) ethers, etheraalcohols (e.g. glycol monomethyl ether, etc'.) amides (e.g. dimethyl formamide, etc.),:sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones. (e.g. actone, etc,,) and/ or water; as well as inert dispersible finely dividedsolid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonatgtalc, kieselguhr,v etc.) ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.), whereas thefollowing may be chiefly consideredfor use as conventional carrier vehicle assistants, e.g. surface-activeagents, for this-purpose: emulsifying agents, such as non-ionc and/or. anionic emulsifying, agents (e.g. polyethylene oxide esters of fatty'acids, polyethylene oxide ethers of.- fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magneslum stearate,. sodium oleate, etc.), and/or dispersing agents,'such as lignin, sul-fite wasteliquors, methyl cellulose, etc. p

Such active compounds may be employed alone or in the form of mixtures with one another and/ or Wllh.'Sl1Cl'1 solid and/or .liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides and insecticides, or fungicides, herbicides, bactericides, etc., if desired, or in -the form of particular dosage preparations for. specific application made therefrom,- such as solu= tions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about (ll-95% by weight, and

preferably 05-90% by Weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0000l-20%, preferably 0.01 to 5%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or -(2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.00001- and preferably 0. 0'l95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-loW-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about '20 to about 95% by weight of active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the activecompou'nd.

In particular, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. arthropods, i.e. insects and acarids, and more particularly, methods of combating at least one of insects and acarids which comprise applying to at least one of correspondingly (a) such insects, (b) such acarids, and (c) the corresponding habitat, i.e. the locus to be protected, "a correspondingly combative or toxic amount, i.e. an arthropodicidally, especially insecticidally or acaricidally, effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular newcompounds of the present invention is illustrated wtihout limitation by the following examples:

EXAMPLE 1 Phaedon larvae test Solvent: 3 parts by weight acetone Emuls'ifier: 1 part by weight al-kylaryl polyglycol ether that all the beetle larvae are killed. means that none of the beetle larvae are killed.

The active compounds, the concentration of the active compounds, the times of evaluation and the results can be seen from the following Table 1.

TABLE I.PHAEDON LARVAE TEST [plant-damaging insects] Concentration Degree of active destruction compound in percent Active compounds in percent after 3 days (A).-- (OHmN O 0.1 0

II /PO a)2 l (known) B (CH) N O 0.1 100 3 z n i 0.01 0

P-O z s) O l 0 O0 cgHs (known) (C) R 0. l 0

(C2H50)IP-O C OO C2H (known) (1)..-- CH 0 0.1 100 ll 0. 01 100 P--O 0.001 100 0. 0001 70 NH:

0 O-0 O3H7i (2).... 011150 0 0.1 100 ll 0. 01 100 PO 0.001 70 NH: l

C O0 C sH1l (3)...- CH3O O 0.1 100 II 0. 01 100 PO 0.001 90 CH3NII C OO Cal-I71 (4).... CgH5O O 0.1 100 ll 0. 01 100 P-O- 0. 001 90 CHs-NH C O-O C3H7i (5).... CzH5O O O. 1 100 H o, 01 100 13-0 0.001 90 NEE-031111 COO CaHfi EXAMPLE 2 Plutella test Solvent: 3 parts by Weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dew moist and are then infested with caterpillars of the diamondback moth (Plutella maculz'pennis).

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the caterpillars are killed whereas 0% means that none of the caterpillars are killed.

CPI

8 The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 2:

TABLE 2.--PLUTELLA TEST [plant-damaging insects] Concentration Degree of active destruction compound in percent Active compounds in percent after 3 days (A)-.- (CHs)2N O 0.1 0

II /1-0 (CH 2N o-o 02H (known) (B)-. (OH0)2N\(]) 006% 38 Q C H O 6 (.L/ O-O C2115 (known) ((3).; S 0. 1 ll 0. 01 0 (C2H O)2PO A, O-O C211 (known) 1 CH O\(H) o 1 1 PO 0. 001 80 Na J3 O-O C H i (2) C2H5 O\(") 00d PO 4? O0 C IHTi CHaO\(H) 0. 1 1

. 1 1 CH3NH L b O O CzHn (4).- CzHaO O 0.1

P-O- CH NE i0 H -NH EXAMPLE 3 Myzus test (contact action) Solvent: 3 parts by weight acetone I Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3:

TABLE 3.-MYZUS TEST [Plant-damaging insects] Concentra- Degree of tions of destruction active in percent compound after 24 Active compounds in percent hours (A). (CHmN 0.1 0

II /P-O s)2N C O-O Cal-I (known) (B).-. (CHahN 0 0. 1

H /PO Cz a l (known) mmonr-o-Q l C 0-0 CgHs (known) 1 CHaO 0 0.1 100 ll 0. 01 99 /PO NH:

(2) CgHnO O 0. 1 98 ll /P0- NH:

0 O O CzHfl 3 0H=0 0 I o. 1 9s ll /P'O CH -NH I 00-0 0311 1 (4).--- CnHsO O 0.1 98

ll /P-0 CHa-NH C O-O 031111 (5)---- CzH5O\() 00.1 01

iCzHz-NH A] 0-0 CaH' l EXAMPLE 4 Tetranychus test Solvent: 3 parts by weight acetone Eniulsi'fier: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately -30 cm., are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that all the spider mites are killed whereas 0% means that none of the spider mites are killed.

10 The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 4:

TABLE 4.TETRANYCHUS TEST [plant-damaging mites] Degree of Concentradestruction tion of active in percent compound after 48 Active compounds in percent hours (A)... (CH3)2N 0 0.1 0

P-O- (CHmN J30 OCH (known) (B).-. (OH3)2N O 0.1 0

O H O 2 f (BO-OCzHn (known) sampl -0Q (known) (1)--.- OH O O 0.1 100 \I i 0.01 90 COOCaH l C2H5o\(l) 0 1 28 l -Q NH2 I 00-00;;H1i (3) CHa'O .0 0.1 \ll,

OH Nfi o-oc mi Ov iCH-NH w 3 rho-0031111 EXAMPLE 5 O OCH:

NHz

\OOOCH(CH3)2 (1) 222 g. (2 moles) of finely powdered selenium dioxide are added in increments to 290 g. (1 mole) of O-methyl- O 2 carbisopropoxyphenyl)-thionophosphoric acid diester amide in 500 cc. of methylene chloride, the reaction temperature rising to 30 to 40 C, Stirring is continued for one hour at 40 C., suction'filtration' of the solids is effected and the solvent is drawn oif in a vacuum. The crystalline residue is recrystallized from a benzeneligroin mixture. 151 g. (55% of the theory)"of O-methyl O (2 carbisopropoxyphenyl) phosphoric acid diester amide of melting point 78 C. are obtained.

The O-methyl-O-(2-carbisopropoxyphenyl)-thionophos phoric acid diester amide used in 'the above example 'as the starting material is obtained 'from 'O-methyl-O (2-' carbisopropoxyphenyl) thionoph'osphoric acid diester monochloride and l5%-strength' ammonia solution. The

1 1 reaction temperature rises to 60 C. After subsidence of the exothermic reaction, the mixture is stirred for a further 24 hours at room temperature. The reaction mixture is then taken up in 200 cc. of benzene and the benzene solution is washed with water until it gives a neutral reaction, dried over sodium sulphate, and the solvent is removed under reduced pressure. The O-methyl-O-(Z- carbisopropoxyphenyl) thionophosphoric acid diester amide so obtained has a melting point of 44 C. Yield: 60% of the theory.

[EXAMPLE 6 o 0,11, ll /O-P \uo-o-cmorrm 2 44 g. (0.4 mole) of finely powdered selenium dioxide are added in increments to 60.6 g. (0.2 mole) of Oethyl- O-(2-carbisopropoxyphenyl)-thionophosphoric acid diester amide in 200 cc. of methylene chloride, the reaction temperature rising to 30 to 40 C. Stirring is continued for 2 hours at 40 C., filtration from the solids is effected and the solvent is drawn off in a vacuum. The crystalline residue is recrystallized from a benzene-ligroin mixture. 36 g. (63% of the theory) of O-ethy1-O-(2-carbisopropoxyphenyl)-phosphoric acid diester amide of melting point 7'1 C. are obtained.

The O-ethyl-O-(Z-carbi'sopropoxyphenyl)-thionophosphoric acid diester amide used in Example 6 as starting material is prepared in a manner analogous to that stated above for the starting material of Example 5. The yield is 76% of the theory; the melting point is 57 C.

In manner analogous to Examples and 6, the following compounds are prepared:

EXAMPLE 7 N isopropyl O ethyl O-(2 carbisopropoxyphenyl)- phosphoric acid diester amide Yield: 71% of the theory; refractive index: n =l.4850

prepared from its thiono analogue S OC H N methyl 0 ethyl O (2 carbisopropoxyphenyl)- phosphoric acid diester amide 12 refractive index: n .=l.525 8 which was prepared analogusly t0 the starting compounds of Examples 5 and 6 in 74% yield.

EXAMPLE 9 N methyl O methyl O (2. carbisopropoxyphenyl)- phosphoric acid diester amide C0 OCH(CH3); (3) Yield: 50% of the theory; refractive index: 12 1.5070

prepared from its thiono analogue S OCH;

CO--O-CH(CHa)2 (IId) refractive index n =1.5254 which was prepared analogusly to the starting compounds of Examples 5 and. 6 in 46% yield.

EXAMPLE 10 O OCQH; o l

To a suspension of 48 g. (0.3 mole) of potassium carbonate in 150 cc. acetonitrile there are added dropwise, at 30 to 40 C., 54 g. (0.3 mole) of salicylic acid isopropyl ester. 55.6 g. (0.3 mole) of O-ethyl-N-isopropylphosphoric acid ester amide chloride are then added slowly to this mixture at 30 to 50 C. Stirring is continued for one hour at 70 C., the solid matter is filtered oil with suction, and the solvent is drawn off in a vacuum. The reaction mixture is taken up in cc. of methylene chloride and extracted with 100 cc. of water. After separation and drying of the organic phase, the solvent is: drawn off in a vacuum. N-isopropyl-O-ethyl-O-(2-carbisopropoxyphenyl)phosphoric acid diester amide is obtained as yellow oil of refractive index n =l.4856. The yield is 86 g. (87% of the theory).

The compounds prepared by the process of Examples 8 and 9 can also be prepared by processes analogous to Example 10 with the following results:

EXAMPLE 11 a/o C211 OP C00-CH(GH 4 Yield: 81% of the theory; refractive index: n =1.5036.

EXAMPLE 12 O OCH;

NH-CH;

Yield: 52% of the theory; refractive index: n =1.5 101.

As may be used herein, the terms arthropod, arthropodicidal and arthropodicide contemplate specifically both insects and acarids. Thus, the insects and acarids may be considered herein collectivelyas arthropods to be combatted in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be 13 termed arthropodicidal activity, and the concomitant combative or eifective amount used will be an arthropodicidal- 1y effective amount which in effect means an insecticidally or'acaricidall'y effective amount of the active compound for the desired purposes.

It. will be appreciated that the instant specification and examples are'set forth by way of illustration and not limitation, and that various modifications and changes may be madeqwit'hout departing from the spirit and scope of the present invention. 7

What is claimed is: p v

1.' O-lower alkyl O (2-carbisopropoxyphenyl) phosphoric acid diesteramides wherein the amide group may be mono-substituted with a lower alkyl radical.

2. Amidophosphorylsalicylic acid esters of the formula in which R is a straight or branched chain lower alkyl radical,

' and k.

IR is hydrogen or a straight or branched chain lower al- 3;' Esters according to claim 2 in which R is an alkyl radical with 1 to 4 carbon atoms and R is hydrogen or an alkyl radical with 1 to 4 carbon atoms.

(Esters according to claim 2 in which R is an alkyl radical with 1 to 3 carbon atoms, and R is hydrogen.

5. Compound according to claim'2 wherein such compound is O methyl- O (2-carbisopropoxyphenyl)-phosphoric acid diester amide of the formula CH O O oo-ocann (1) 6. Compound according to claim 2 wherein such compound is O-ethyl-O-(2-carbisopropoxyphenyl)-phosphoric acid diester amide of the formula o-oomn 7. Compound according to claim 2 wherein such compound is N-methyl O methyl-O-(Z-carbisopropoxyphenyl) phosphoric acid diester amide of the formula CH O 0 8. Compound according to claim 2 wherein such compound is N-methyl-O-ethyl-O-(Z-carbisopropoxyphenyD- phosphoric acid diester amide of the formula on N fro-0031111 9. Compound according to claim 2 wherein such compound is N-isopropyl-O-ethyl-O-(2-carbisopropoxypheny1)-phosphoric acid diester amide of the formula" JOSEPH REBOLD, Primary Examiner A. H. SU'ITO, Assistant Examiner U.S. Cl. X.R. 260-985; 424-220 u. Luv-u.

292 33 UNITED STA'IISS IA'LISN'I"bI FICE QERTIFICATE OF CORRECTION Patent No. 3,660, 40 I mired May 1972 lnvcn tox-(s) Wolfgang Hofer et a1 It is certified that error aypcars in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

601. 2 line 60 Diagrafn' l "CO-O-CH" shouldread "co-o-cr 1'(c ;H'

Col wlgne 2O 1 "'SimeX should be f'bimex" C61. 5 line 2 Opening parenthesis s-houldbe' ineert ed before 'YT'etrariychidae C01 9, Table 3, Ex; B

U nder the "Degree of destitpctioh ih Z, after 24 hours','

column', 't he f'e. should'be e- C51. 12, line 53., EX. 11

- "n II I n y .oc g 511011 1 1 be 00 5 I l Signed a nd --seale'd t h i's s 28th day of No fembe r 1 972.

' (SEAL) LAtte'st:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK I Attestlng OfflCBI Commissioner of Patents I 

